{"id":{"repo_id":"columbia-diss","oai_identifier":"oai:academiccommons.columbia.edu:10.7916/D8ZG70KT"},"canonical_url":"https://search.dev.ndltd.org/etd/columbia-diss/oai:academiccommons.columbia.edu:10.7916/D8ZG70KT","repository":{"repo_id":"columbia-diss","name":"Columbia University","base_url":"https://academiccommons.columbia.edu/oai"},"display":{"title":"A 'Toolkit' of Small Molecules for Polymer Assembly and Post-Synthetic Modification Using 'Click' and Photoactive Chemistries","abstract":"Small molecules have been synthesized toward the goals of constructing and modifying polymeric materials according to simple, generalizeable, and universal processes. The prepared compounds rely upon a combination of photochemistry and the 'click' philosophy to alter the architecture, bulk properties, or surface chemistry of polymers. In Chapter 1, a review is presented that details the many implementations of the 'click' philosophy to polymer chemistry. The influence of 'click' and photochemistry upon macromolecules is discussed using a topological approach to polymer architecture. Chapter 2 details the synthesis of several second-generation homobifunctional exogenous photocrosslinkers that extend upon previous work from our group. Additionally, a first-generation crosslinker is used to core-crosslink micellar aggregates of block copolymers. Chapter 3 describes the design, synthesis, and implementation of a photoactive 'click' activator for polymer surfaces. This chapter extends the notion of a material-specific anchor from hard substrates to a range of soft polymer substrates. Chapter 4 is an inquiry into the nature of the photoreaction of a standard photoactive moiety - benzophenone - with model compounds that represent polymers in which the crosslinkers of Chapter 2 are embedded. Comparison of competitive rates of abstraction gives insight into the reactive preferences of the crosslinkers and anchors of the previous chapters. In Chapter 5 small molecules and macromonomers are described that build upon the compounds described in previous chapters which collectively form the basis of a 'toolkit' approach to polymer assembly and modification. Variations and extensions upon the 'toolkit' are detailed in order to give a sense of the future possibilities of this approach.","abstract_html":"Small molecules have been synthesized toward the goals of constructing and modifying polymeric materials according to simple, generalizeable, and universal processes. The prepared compounds rely upon a combination of photochemistry and the 'click' philosophy to alter the architecture, bulk properties, or surface chemistry of polymers. In Chapter 1, a review is presented that details the many implementations of the 'click' philosophy to polymer chemistry. The influence of 'click' and photochemistry upon macromolecules is discussed using a topological approach to polymer architecture. Chapter 2 details the synthesis of several second-generation homobifunctional exogenous photocrosslinkers that extend upon previous work from our group. Additionally, a first-generation crosslinker is used to core-crosslink micellar aggregates of block copolymers. Chapter 3 describes the design, synthesis, and implementation of a photoactive 'click' activator for polymer surfaces. This chapter extends the notion of a material-specific anchor from hard substrates to a range of soft polymer substrates. Chapter 4 is an inquiry into the nature of the photoreaction of a standard photoactive moiety - benzophenone - with model compounds that represent polymers in which the crosslinkers of Chapter 2 are embedded. Comparison of competitive rates of abstraction gives insight into the reactive preferences of the crosslinkers and anchors of the previous chapters. In Chapter 5 small molecules and macromonomers are described that build upon the compounds described in previous chapters which collectively form the basis of a 'toolkit' approach to polymer assembly and modification. Variations and extensions upon the 'toolkit' are detailed in order to give a sense of the future possibilities of this approach.","abstract_has_math":false,"creators":["Lancaster, Jeffrey R."],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011","date_published":"2011","updated_at":"2026-07-24T01:44:32Z","subjects":["Chemistry","Polymers","Chemical engineering"],"languages":["English"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://doi.org/10.7916/D8ZG70KT","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Lancaster, Jeffrey R."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011"]},{"key":"dc:type","label":"Dc Type","values":["Theses"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry","Polymers","Chemical engineering"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://doi.org/10.7916/D8ZG70KT"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Small molecules have been synthesized toward the goals of constructing and modifying polymeric materials according to simple, generalizeable, and universal processes. The prepared compounds rely upon a combination of photochemistry and the 'click' philosophy to alter the architecture, bulk properties, or surface chemistry of polymers. In Chapter 1, a review is presented that details the many implementations of the 'click' philosophy to polymer chemistry. The influence of 'click' and photochemistry upon macromolecules is discussed using a topological approach to polymer architecture. Chapter 2 details the synthesis of several second-generation homobifunctional exogenous photocrosslinkers that extend upon previous work from our group. Additionally, a first-generation crosslinker is used to core-crosslink micellar aggregates of block copolymers. Chapter 3 describes the design, synthesis, and implementation of a photoactive 'click' activator for polymer surfaces. This chapter extends the notion of a material-specific anchor from hard substrates to a range of soft polymer substrates. Chapter 4 is an inquiry into the nature of the photoreaction of a standard photoactive moiety - benzophenone - with model compounds that represent polymers in which the crosslinkers of Chapter 2 are embedded. Comparison of competitive rates of abstraction gives insight into the reactive preferences of the crosslinkers and anchors of the previous chapters. In Chapter 5 small molecules and macromonomers are described that build upon the compounds described in previous chapters which collectively form the basis of a 'toolkit' approach to polymer assembly and modification. Variations and extensions upon the 'toolkit' are detailed in order to give a sense of the future possibilities of this approach."]},{"key":"dc:title","label":"Title","values":["A 'Toolkit' of Small Molecules for Polymer Assembly and Post-Synthetic Modification Using 'Click' and Photoactive Chemistries"]}]}],"canonical_facts":{"dc:creator":["Lancaster, Jeffrey R."],"dc:date":["2011"],"dc:description":["Small molecules have been synthesized toward the goals of constructing and modifying polymeric materials according to simple, generalizeable, and universal processes. The prepared compounds rely upon a combination of photochemistry and the 'click' philosophy to alter the architecture, bulk properties, or surface chemistry of polymers. In Chapter 1, a review is presented that details the many implementations of the 'click' philosophy to polymer chemistry. The influence of 'click' and photochemistry upon macromolecules is discussed using a topological approach to polymer architecture. Chapter 2 details the synthesis of several second-generation homobifunctional exogenous photocrosslinkers that extend upon previous work from our group. Additionally, a first-generation crosslinker is used to core-crosslink micellar aggregates of block copolymers. Chapter 3 describes the design, synthesis, and implementation of a photoactive 'click' activator for polymer surfaces. This chapter extends the notion of a material-specific anchor from hard substrates to a range of soft polymer substrates. Chapter 4 is an inquiry into the nature of the photoreaction of a standard photoactive moiety - benzophenone - with model compounds that represent polymers in which the crosslinkers of Chapter 2 are embedded. Comparison of competitive rates of abstraction gives insight into the reactive preferences of the crosslinkers and anchors of the previous chapters. In Chapter 5 small molecules and macromonomers are described that build upon the compounds described in previous chapters which collectively form the basis of a 'toolkit' approach to polymer assembly and modification. Variations and extensions upon the 'toolkit' are detailed in order to give a sense of the future possibilities of this approach."],"dc:identifier":["https://doi.org/10.7916/D8ZG70KT"],"dc:language":["English"],"dc:subject":["Chemistry","Polymers","Chemical engineering"],"dc:title":["A 'Toolkit' of Small Molecules for Polymer Assembly and Post-Synthetic Modification Using 'Click' and Photoactive Chemistries"],"dc:type":["Theses"]},"updated_at":"2026-07-24T01:44:32Z"}